Bleach-fabric softener compositions

ABSTRACT

CONCENTRATED, DRY BLEACH AND FABRIC-SOFTENING COMPOSITIONS CONTAINING A PEROXYGEN BLEACHING AGENT, A QUATERNARY AMMONIUM COMPOUND, A BUFFERING AGENT AND IONIZABLE CHLORINE. SUCH COMPOSITIONS WHEN DISSOLVED IN WATER PROVIDE FAST-ACTING CATALYZED BLEACHING AND SOFTENING OF TEXTILES AT ALL PRATICAL SOLUTION TEMPERATURES WITHOUT THE COLOR AND FABRIC DAMAGE USUALLY ASSOCIATED WITH HARSH HYPOCHLORITE BLEACHES.

2:11UE5-0l on July 31, 1973 J. P. JONES ETAL 3,749,673

BLEACH-FABRIC SOF'IENER COMPOSITIONS Filed Feb. 22. 1971 EFFECT OF TIMEAND TEMPERATURE ON BLEACHING 9 I20 OFHHO) 80F. (#II) II b I20 F(#l3)80F. (#13) 3 l l I l l Time (min.)

INVENTORS John Paul Jones Charles H. Nicol MW A TURNEY Int. Cl. Clld7/54 U.S. Cl. 252-95 8 Claims ABSTRACT OF THE DISCLOSURE Concentrated,dry bleach and fabric-softening compositions containing a peroxygenbleaching agent, a quaternary ammonium compound, a buffering agent andionizable chlorine. Such compositions when dissolved in water providefast-acting catalyzed bleaching and softening of textiles at allpractical solution temperatures without the color and fabric damageusually associated with harsh hypochlorite bleaches.

BACKGRQQND @F INVEN IQN Field o th nven ion Thi inven ion re ates is d yhs ash conincsitiens liarii b "s fishin an on solarilaiiiess hlsashiiigsha a is 'ish s when shin l in aqueous sols sh resinous may lso he usedfornd for r stor n natura lo, a ti i ial hair c lqr na As ii. ed, theseA it c in the m Bi 2 ca flied PWdUQi Wlllll aii he added to Weir-i oactua l, at both high and low bleaching t mp atu es Th in en ion employsii combination o a Peron/gen achin compound; quaternary ammonium salt amicelle catalyst and fabric softenerf a buffering COIIPDI l'ld tomaintain the bleaching solution at a proper p p izable chlorine toprovide a type of halogen bleach referred m od me s emp y n a kal m t lor al s earth met l hloride salt to provide t e a p r on e the ionlzablechlorine. Additional preferred embodiments mp oy a 'll l whi h w llprovide t ansi ion metal n h s ca aly i in mind While a ing micellecatalyst for the inc-aching 11?. action, the qua erna ry ammonium retaintheir fabric softening capabilitie" and can also provide a. source of:necessary chloride ion 1 h non quai rnm'y chl r de QlIl pounds leg.alkali metal or alkaline earth metal f lllon ides) on t be employed inthe pr '11? compositions to provide chloride ions if the quad noniumcom: pound does not movide these ion in s 7 nt concentrav iion.Inclusion :l the ll an" dry compos ons of a source of transition metalions is not. tial to the invention but enhanced bleacl'ling performanceis obtained it such source cornponruj is; employed,

pounds are effective stain-removing b r ilil lfifi when 1 4 hi I velyhigh conccntratio chl 1 Q1 a in chlorine bicacl'ies o ruse rather severedamage to fabric colors and can in addition damage textile fibr ls withrepeated use. Liquid bleachesof this type also pre- 3,749,673 PatentedJuly 31, 1973 sent handling and packaging problems. While color andfabric damage may be minimized by employing milder oxygen bleaches suchas potassium monopersulfate, soil and stain removal characteristics ofthese oxygen bleaches are much less desirable than those of the halogenbleachlng agents.

Likewise, several types of fabric softeners are presently available forhome use, but all must be added separately to the fabric rinse solutionsince they are chemically incompatible with many laundering products.

Many of the above-described shortcomings of prior art compos tions areovercome by a chlorine-free bleaching composition described in theconcurrently filed application of John Paul Jones and Charles H. Nicolentitled Bleach Compositions, Ser. No. 117,814, filed Feb. 22, 197 l. Itis an object of the present invention to provide an improvedconcentrated chlorine-containing bleaching composition which can besafely applied to colored as Well White fabrics= It is a further shiestof this inven: h m is provide eornsatihle hlseshiah'ric softener cohinatios which is m d in the form oi s ls shit i ls i it is furtheronset of the i mvenon is provide 2 catalyzed hlashiah q when which hashe 'l sd at low so he was alien and wh' h is eiieciive a law tsiiieshires and. after short is M Whi e b each and fab. taiiiing cs sin o theabm :1. mm. s v been disclosed in the prior art it h .i now bee ihiithycombining ssriaintypssofca .l hated bleaching agents, a so ed aching ataboo softening p oduct can be created whish accomp ishes he above ohsilvers and which i uneiipestedly SUP TlQTiQ that attainable using thescmpositions of the prior art SUMMAR OF HE VEN IQN D S Q l fi fil d, haqh fabric Softener compositions and me hods for u ing said compo tionar provide e compo iti ns c nsi s n ially of:

(a) about 8% to 60% by eight of a. peroxy bleaching agent selec ed fromth group onsis fi o sodium r potassium monopei' ulfate; organ p nny aids in wa el s luh e s ts th eof) of the e eral f rm l QIJQHT- 10% to60% of a qu ifimnry ammonium com pound of th g neral form la wherein Ris an alkyl group containing from about 12 to 20 carbon atoms, R isselected from the group consistingof alkyl groups containing about 1 to14 carbon atoms, cycloalltyl groups containing about to 8 carbon atoms,carboxymethyl groups, aryl groups 5 containing from 6 to 8 carbon atoms,alkaryl groups containing from 7 to carbon atoms, pyridyl and groups ofthe general formula -(C H O),,(C H,O) H wherein a and b are integers anda+b is 1 to 50; R R and R are each selected from the group consisting ofalkyl groups containing about 1 to 3 carbon atoms, cycloalkyl groupscontaining about 5 to 8 carbon atoms, carboxymethyl groups, aryl groupscontaining from 6 to 8 carbon atoms, alkaryl groups containing fromabout 7 to 10 carbon atoms, pyridyl, and groups of the general formula(C H O) (C H O) H wherein a and b are integers and a+b is 1 to 50; R isa group within the definition of the R R and R groups or H; R; is analkylene group containing from 1 to 3 carbon atoms, an arylene groupcontaining from 5 to 8 carbon atoms or a group having the formula saidcompositions containing from about 5 to about 100 grams of ionizablechlorine per kilogram of the total composition. The compositions cancontain from about 1% to 15% by weight of an alkali metal or alkalineearth metal chloride to provide all or part of the ionizable chlorine.Alternatively, all of the ionizable chlorine can be provided by thequaternary ammonium compound as hereinafter detailed. A preferredembodiment of the invention contains, in addition to the abovecomponents, from about 0.08% to about 8% by weight of a watersolublesalt of a transition metal element.

The compositions are dissolved in water to provide fabric softening andcatalyzed bleaching of both colored and white fabrics. Such aqueoussolutions may also be used as hard surface or denture cleaners and asagents for restoring natural color to artificially colored hair.

BRIEF DESCRIPTION OF THE DRAWING The drawing provides a graphicalrepresentation of the elfect of time and temperature upon the bleachingactivity of the compositions of the instant invention relative to theprior art. The horizontal axis represents time in minutes. The verticalaxis represents AW, a measure of stain removal performancedescribed incolumn 9, lines 73-75, hereof. Each curve represents a particularbleaching composition of Table I (col. 9) identified by number andutilized at the indicated temperature.

DETAILED DESCRIPTION OF THE INVENTION At this juncture the theoreticalnature ofthe present catalyzed bleaching system and the individualcomponents of the compositions will be described in detail.

(A) Catalysis of bleaching reactions Although the scope of the presentinvention is not limited by any particular theory, the monopersulfatebleaches of this invention are believed to ionize in the bleachingsolution according to the equation KHSO =K++HSO The HSO furtherdissociates in solution as follows:

'HSO 1 *H++SO It has been discovered that the etfectivenessho f-rtheper-- sulfate-bleaching is dependent on the formatio insolm tion of abi-anionic transition state complex having the formula Such a complex isformed from the SO and H80 anions present in the bleaching solution.

The organic monoand diperoxyacid bleaches of the instant compositions,representative compounds having the general formulas,

wherein R is an alkylene or arylene group, likewise form bianionicdimers during the bleaching process. As with the monopersulfates, suchcomplexes are formed from the combination of (l) the above compoundswhich have lost one proton upon dissolution and/or (2) the abovecompounds which have lost both protons. Thus, these bianionic complexes,for example, can have the general formulas,

or if the above two representative compounds are mixed,

O 0 O O a. [-o-o-dR- ioo Ho oii-R Ji0-] wherein R is again an alkyleneor arylene group.

It has been discovered that formation of these various complexes fromtwo negatively charged ions can be facilitated by the addition to thesolution of positively charged micelles and/ or transition metal ions.

A micelle' is a highly charged colloidal aggregate. It is believed thatsuch positively charged aggregates, as well as positive transition metalions, serve as rallying points for the S0 and HSO anions and theirorganic peroxyacid counterparts, thereby facilitating formation of theindispensible transition complex of the bleaching reaction. Quaternaryammonium salts are employed in order to form the necessary miceslles insolution. In addition, bleaching catalysis may be enhanced by additionof a transition metal salt such as copper sulfate, to provide morecomplex-creating cations in solution.

Bleaching activity is enhanced even further by virtu-re of chloride ionsin bleaching solutions. Consequently, dry compositions of the presentinvention must contain enough of a water-soluble chloride compound ormixtures thereof to provide from about 5 to about grams of ionizablechlorine per kilogram of dry composition. Ionizable chloride is thatportion of any compound of the present invention which when dissolvedcontributes chloride ions to the aqueous solutions. Ionizable chlorineis, of course, provided by chloridesalts. The necessary ionizablechlorine content of the instant composition can be provided in the formof the quaternary ammonium chloride, an added alkali metal or alkalineearth metal chloride and/or by the transition metal chlorides. It isknown that these chloride salts in solution with certain oxygen bleachesdo not yield chloride ions but rather, in combination with such oxygenbleaches, provide enhanced bleaching of a hypochlorite type. It has beendiscovered, however, that addition of chloride ions to amicelle-catalyze'd oxygen bleaching system yields an active chlorinespecies in solution to provide mixed oxygenchlorine bleaching even moreeffective than the known hypdchloriteforming peroxygen/chloride saltcombination..-, Furthermore,-= this etfective bleaching is acco solutionthan, prior art hypochlorite-forming combinations.

It is believed that the effective micelle catalysis of the bleachingreaction is responsible for the very favorable color damagecharacteristics of the instant compositions. Although some hypochloriteis formed in solution from the compositions of the instant invention, itis formed over an extended period of time and at a lower concentrationthan the directly added hypochlorite of the prior art. Performance lossdue to this indirect method of hypochlorite bleaching is more thanadequately compensated for by the effectiveness of thernicelle-cattalyzed oxygen bleaching. Overall bleaching performance thuscompares favorably with harsh concentrated hypochlorite with littlehypochlorite-type color damage occurring.

It should be noted that the compositions of the instant invention shouldcontain no more bromide than would be present if the optional transitionmetal salt is a bromide. This is so since large amounts of bromide ionsin solution with some peroxygen bleaches can cause severe color damageto fabrics. Consequently, the quaternary ammonium compound (which can bepresent in a relatively high concentration in the composition) cannot bea bromide salt, i.e. bromide is an interfering anion.

(B) Individual components (1) Bleaching agents.The principal bleachingactive-s in the instant compositions are sodium or potassiummonopersulfate (NaHSO and KHSO and the organic monoand diperoxyacids (orwater-soluble salts thereof) having respectively the following formulas:

O MONOPEROXY ACID HO C-RYH and O O DIPEROXY ACID wherein R can bealkylene or arylene and Y can be any group which yields an anionicmoiety in solution such as Potassium monopersulfate is availablecommercially from E; I. du Pont de Nemours and Company under the tradename Oxone. It contains aproximately 42.8% by weight KHSO the balancebeing KHSO and K 80 in about equal proportions.

The organic peroxyacids or salts thereof of the invention, as notedabove, can contain either one or two peroxy groups and can be eitheraliphatic or aromatic. When the organic peroxyacid is aliphatic, theunsubstituted acid has the general formula where Y, for example, can beand n can be an integer from 1 to 12 with perazelaic acids (n=7) beingthe prefer-red compounds. The alkylene linkage between the anionicgroups can contain halogen or othe non-interfering groups.

When the organic peroxyacid is aromatic, the unsubstituted acid has thegeneral formula Where Y is for example. The

and YH groupings can be in any relative position around the aromaticring. The ring can contain any noninterfering substituent such ashalogen groups. Examples of suitable aromatic peroxy acids includemonoperoxyphthalic acid, dip-eroxyterephthalic acid,4-chlorodiperoxyphthalic acid and the monosodium salt ofdiperoxyterephthalic acid. The preferred aromatic peroxyacids are themonoand diperoxyisophthalic acids.

The bleaching compositions can contain from about 8% to about 60% byweight of the bleaching agent. The preferred monopersulfate weight rangeis from about 25% to about 30% by weight. A preferred organic peroxyacidweight range is from about 16% to about 35% by weight. Mixtures of themonpersulfate compounds and the peroxyacids can be employed in theinstant invention. These bleaching compositions are, of course,dissolved in aqueous solutions for actual use on fabrics, sinks,dentures or hair. Dependin upon the bleaching strength desired and theintended use, the bleaching composition is added in quantitiessuflicient to yield from about 5 to ppm. available oxygen in solutionfrom either the persulfate or organic peroxyacid bleach actives. Theabove bleaching actives when employed in the catalyzed compositions ofthe present invention provide effective bleaching at all practicalbleaching solution temperatures and bleach effectively after a. veryshort contact time with the material to be bleached. As noted, color andfabric damage is minimal.

(2) Quaternary ammonium compounds-Quaternary ammonium compounds usefulherein have the general formulas and Ilia lla Rr-III-Ih-III-Rg R: R5

[ -his wherein R is an alkyl group containing from about 12 to 20 carbonatoms, R is an alkyl group of about 1 to 14 carbon atoms, a cycloalkylgroup of about 5 to 8 carbon atoms, a carboxymethyl group, a 6 to 8carbon aryl group, an alkaryl group of 7 to 10 carbon atoms, a pyridylgroup, or a group of the general formula either a 1 to 3 carbon atomalkylene group, a 5 to 8 carbon arylene group or a group of the formulaX is any non-interfering anion such as chloride, nitrate, fluoride,sulfate, methylsulfate, carbonate, hydrogen phosphate, dihydrogenphosphate, chlorate or hydroxide; and n is 1 when X is monovalent and nis 2 when X is divalent. Examples of quaternary ammonium compoundsemployable in the compositions include tetradecyltrimethylammoniumchloride; tetradecyltrimethylammonium methylsulfate;tetradecyltrimethylammonium nitrate; cetyltrimethylammonium hydrogenphosphate;

[C16H35N 3 a 1 2 4;

cetyltrirnethylammonium nitrate; octadecyltrimethylammonium chloride;octadecyltrimethylammonium chlorate; octadecyltrimethylammonium nitrate;eicosyltrimethylammonium chloride; eicosyltrimethylammonium hydroxide;eicosyltrimethylammonium nitrate;

[C20H39N(CH3)3[2HP04, the ethylbenzyl ammonium chlorides of Petrocci etal., US. Pat. 3,525,793, Aug. 25, 1970; Armour Industrial ChemicalCompanys Ethoquad and Propoquad and singly or doubly quaternizedcompounds derived from Wyandotte Chemical Corporations Tetroniccompounds. Preferred quaternary ammonium compounds are the C C and Calkyltrimethylammonium chlorides. Depending upon the particularquaternary ammonium compound employed, the compositions contain fromabout 10% to about 60% by weight of the quaternary ammonium component.

The quaternary ammonium constituent serves two purposes in the instantcompositions. These surface active compounds form the micelles forcatalysis of the peroxygen bleaching, and in addition they impart fabricsoftening characteristics to the bleaching solutions. In solutionsprepared from the compositions of this invention the quaternary ammoniumsalt concentration should range from about 100 p.p.m. to about 500p.p.m.

It is well-known that quaternary ammonium compounds of the type hereinemployed function as fabric softeners. They have heretofore beenutilized alone in laundry rinse water since they are incompatible withanionic detergents. It has been discovered, however, that thesecompounds are compatible with the bianionic, complex-forming bleachagents of the present invention and, in fact, act as micelle catalystswhile retaining their fabric softening properties.

It has been found that the shorter chain quaternary ammonium salts (Cprovide slightly better micelle catalysis while the longer chain saltsC1840 are better fabric softeners. Conseqeuntly, a mixture of long andshort chain quaternary ammonium compounds is preferred for use in theinstant compositions. Thus a preferred embodiment of the invention is adry composition which contains about 2% to about 30% by weight of acarbon chain quaternary ammonium salt and about 8% to 30% by weight of14, 16 or 18 carbon chain quaternary ammonium salts. In aqueous solutionprepared from this preferred composition there should be from about 20p.p.m. to about 80 p.p.m. of the C1840 quaternary ammonium salt toprovide softening capability. As discussed more fully below, thequaternary ammonium compound, if a chloride salt, can contribute to thetotal required ionizable chlorine content of the composition.

(3) Buffering agent.-It has been discovered that micelle catalysis andformation of the bianionic complexes discussed above are greatlyfacilitated by maintenance of the bleaching solution at a carefullycontrolled pH. The pH of the solution at which the concentration of theSO and HSO]- anions are equal (the pK/,) occurs at apH of 9.2 The pK/ofth'eorganic peroxyacid'systemf from'a' pH of 7 to Consequentlythe bestbleaching performance occurs when the pH of the bleaching solution ismaintained between about 7 and about 10. Outside this pH range,bleaching performance diminishes markedly.

To maintain this controlled pH in solution, any noninterfering compoundwhich can alter and maintain pH such as any standard buffering agent orcombination is employed. For example, phosphates, carbonates orbicarbonates which buffer within the 7-10 pH range are useful. Examplesof suitable buffering agents include sodium bicarbonate, sodiumcarbonate, disodium hydrogen phosphate and sodium dihydrogen phosphate.Sodium carbonate is the preferred buffering agent for monopersulfatesystems. Disodium hydrogen phosphate and sodium dihydrogen phosphate arepreferred for peroxy acid systems. Other buffering compositions for anydesired pH can be obtained by the skilled artisan from any standardchemistry handbook or textbook. Buffering agents comprise from about 10%to about 75% by weight of the compositions.

(4) Alkali metal or alkaline earth metal chl0ride. Addition of acompound of this type to the concentrated bleaching composition of thisinvention is optional if the quaternary ammonium compound is a chlorideand is present in the dry compositions in sufiicient amount to providethe necessary 5 to grams of ionizable chlorine per kilogram of the totalcomposition. If, however, the quaternary ammonium compound is not achloride or is not present in an amount sufiicient to provide the properionizable chlorine content, this alkali metal or alkaline earth metalchloride is a necessary component. Suitable chlorides include, forexample, NaCl, KCl, C-aCl and Mgclg.

When the alkali metal or alkaline earth metal chloride is employed, itshould comprise from about 1% to 15% by weight of the total composition.In general, preferred embodiments of the present invention employ enoughchloride compound of any type so that in solution the chloride ion,(although as noted above, the chloride ion as such probably does notexist in the bleaching solution) is present from whatever source in atheoretical p.p.m. amount equal to the p.p.m. of available oxygen (av. 0from the oxygen bleaching actives. A more specific preferred embodimentof the present invention would employ a quaternary ammonium chloride ofthe type defined above in an amount of from about 15 to about 25% byweight with an alkali metal or alkaline earth metal chloride compoundbeing present in a concentration of from about 2% to about 10% byweight.

(5) Transistion metal salt.Improved bleaching can also be obtained bythe optional addition to the compositions of a source of transitionmetal ions. Any soluble salts which yield such ions in bleachingsolution are useful in this invention. Such ions are believed to furthercatalyze the formation of the active peroxy compound and chlorinespecies to provide synergistic bleaching enhancement.

Transition metal salts which can be used in the instant compositionsinclude copper sulfate, copper chloride, cobalt chloride, manganesebromide, nickel nitrate, copper nitrate, chromium chloride, manganesenitrate and chromium bromide. It should be noted that if chloridetransition metal salts are employed, they also can contribute to thenecessaary ionizable chlorine content of the compositions.

Such transition metal salts can be employed in the present compositionsin a concentration range of from about 0.08% to about 8% by weight. Thesalts are preferably present in an amount efifective to provide atransition metal ion concentration in bleaching solution of from about 510- M to about 3 10 M.

(6) Other additives.0ther optional additives such as builders, perfumes,coloring agents, fillers, etc., .can be added to the dry bleaching andsoftening compositions.

These additional components, however, must not interfere with theessential chemical or physical functioning of the compositions ascatalyzed bleaches and fabric softeners.

The above-described components of the bleaching compositions of thisinvention are all available in dry form.

10 (grass, tea, wine, gravy and Empa-Sulfur Black). A AW difference of 2is readily apparent to the human eye.

PREPARATION OF STAINED SWATCHES Formulation, therefore, of drycompositions s Simply The swatches used in the development of thesetests accompllshed y thoroughly {mxmg the gr anu1ar or are obtained fromseveral sources. The respective swatches powdered components together inthe appropriate weight and their Sources (commercial or method ofprepara percentage concentrations. It would be possible to tion) areoutlinedin the following Summary provide a bleaching solution containingthe components of this present invention by adding such components tothe Grass stain bleaching solution in liquid form. Besides creatinghandling and packaging problems, however, concentrated liquid gg gfi j gi i wlth i g ofdthis type ariirelatively unstable and tend until auniforri slirr y i s pi' t lii il iiiis slu3 5 i: s iiz i ri d to rapi yegra e upon stan ing.

of cata ze ox en-c orine a ents erein, textl e er damayge is cogiarableto pergborate washing agents In suctilessve times. The cloth is agedthree days and stored addition, the bleaching solution resulting fromthe commt e positions of the present invention do not cause running Teaof textile colors or undesirable color transfer. The fastacting lowtemperature bleaching activity of the dissolved gli gi zi g xgg s igiggfg zfi gg g g f compositions makes the present invention especiallysuited The solution is filtered through cotton cloth and H for use infabric rinse water after normal textile laundering. made up to 11/2gallon with hot Water Two S are ds The following tests serve toillustrate the bleaching, of cotton are immersed into the teasocllutionyThe Softening and other performance Properties of thetemperature is raised to boil and maintained for two positions of theinstant invention. Table I provides 16 hours The cloth is lifted out ofthe liquor and trans concentrated bleaching compositions by componentweight f d to about 3 gallons of 5 grjgal. water (pH=9.5) percentagescomposlilons 12 at 100 F. to rinse. Wringing is done using the Atlas and15 are representative examples of compositions of the Electric PadderThe cloth is ironed to fix the stain and instant invention. CompositionNo. 8 contains dihydroanowedtoalgefrthreedaysat120,, F genated tallowammonium monoperoxysulfate. Composition No. 11 is a hypochloriteformulation. Composition Gravy No. 16 is a potassiumdichloroisocyanurate composition. The others are compositions with oneor more of the essenoneounce Package of Durkees brown Y miX is tialcomponents of the instant invention omitted. These Wlth 1 P of Water andbrought t0 a boil With compositions are employed in the followingBleaching stirring. Tllfl mixture is removed Il'Om the heat and stirredPerformance Test. Color Damage Test, Bleaching Time With a high-Shearhomogenilef for 5 inutes- The warm and Temperature Test, and FabricSoftening Test. gravy solution is then placed in a container and thecloth TABLE I Y Concentrated composition number 1 2 3 4 5 6 7 8 9 10 ll12 13 14 15 16 Component, weight percent:

Potassium monopersulfate 27 29 25 27 31 18 25 Diperazelaic acidMonoperoxyphthalic acid- Dlperoxyisophthalic acid Dihydrogenated tallowammonium monoperoxysnlfatp Sodium hypochlorite Potassiumdichloroisocyanurete Elcosyltrimethylammonium chloride.Octadecyltlimethylammonium chloride Cetyltrimethylammonium chorideEthoquad 18/12 1 Cetyltrimethylammonium nitrate 14 38 Sodium choride 10Chloride ion content (g. Cl-lkg. composition) 16.8 35 2 0 15 5 63 19 515 5 Copper sulfate- Butler". 22 21 12 20 20 22 2a 15 26 20 22 26 15 20Inerts 37 36 29 30 15 38 40 13 33.82 94. 75 36.8 43 25 33.8 85 See thefollowing formulawherein R is stea yl and the compound contains 2 molescombined and the color differences, AW, so obtained were taken as ameasure of stain removal performance. The average AW values for fivestains are reported in the example ethylene oxide and has a molecularweight of 422. See Armour Industrial Chemical Company Technical BulletinF-4.

For Compositions 1, 2, 4 6, 7, 8, 10, 12, 13, 14 and 15 the bufferingagent s sodium carbonate. For Compositions 2, 5 and 9 the bufien'ngagent is a mixture of dlsodium hydrogen phosphate and sodium dihydrogenphosphate in a NazHPO; to N8H2PO4 ratio of approximately 5:1.

is run through the solution and padded. The stained cloth is then driedin an oven. Two applications are given.

Empa-sulfur black and red wine These cloth samples are obtainedcommercially from Test Fabrics Inc., 55 Vandam St., New York 13, N.Y.,manufactured by E.M.P.A., Unterstasse II, 9001 St. Gall, Switzerland.

BLEACHING PERFORMANCE TEST Bleaching activity of Compositions of Table Iis compared. Table II provides the concentration in bleaching solutionof components of the various compositions. Table II also summarizes theAW value of each composition, thereby indicating their relativ bleachingperformance.

'tained.

When the cetyltrimethylammonium nitrate of Com--..-

TABLE II Concentrated composition number 3* Component-solutionconcentration:

Potassium monopersuliete (p.p.m. av. 09-.-"--- Diperazelaic acid (ppm.av.

Sodium chllfoit-idzibgpdn ii) 100 Copper a e Initial Solution pH 9. 310.0 12. 3

AW Color damage index 1 See Table I, footnote 1.

These compositions were used after or as the cloths were washed'in Tide"at 125 F. with 7 grain/gallon hardness water.

It can be seen from Table II that the compositionsof the instantinvention provide stain removal superior to the other prior artcompositions at comparable strength in solution and superior tocompositions not containing all of the essential components of theinstant invention. Preferred Composition No. performs at a very lowstrength about as well as a highly concentrated NaOCl bleaching solution(No. 11).- Substantially similar AW results are obtained with thecompositions of the present invention not appearing in Table 11 (Nos. 5and 9).

When the potassium monopersulfate of Compositions 2, 4, 6, 10, 12 and isreplaced with sodium monopersulfate and when the diperazelaic acid ofComposition 3 is replaced with monoperazelaic acid, substantiallysimilar performance results are obtained.

When the diperoxyisophthalic acid of Composition 9 is replaced withdiperoxyterephthalic acid, 4-chlorodiperoxyphthalic acid, the monosodiumsalt of diperoxymonium fluoride, sulfate, methylsulfate, hydrogenphosphate, dihydrogen phosphate, chlorate, carbonate or hydroxidesubstantially similar performance of the compositions is obtained.

COLOR DAMAGE TEST Color damage characteristics of the compositions ofthe instant invention are compared to each other and to the othercompositions of Table I. Color damage is ascertained and evaluated bythe following procedures. Thirtytwo difierent articles of clothinghaving characteristics summarized in Table III are first washed in Tide,a representative commercially available laundering detergent, with waterof 7 grain hardnessat 125 F. Compositions 11 and 16 were employed in thewash water itself. The other compositions were utilized in 7 grainhardness rinse water at 100 F. All compositions were employed at theconcentrations of Table II.

TABLE III.CLOTHING USED FOR COLOR DAMAGE TEST Fiber content Color ItemBrand Cnttnn Yellow Girl's dress Bonnie Press.

Do Blue Sheet Wamsutta Lustercale.

Do Turquo Towel Stevens Utica.

Do Green Girl's dress. Bonnie Press.

Do B1uck Man's Slacks Wrangler.

% polyester/50% cotton- Turquoise Child's shirt- True Merit.

D0 do Womans skirt Donnkenny. Polyester Yellow Woman's shelL- Sweetree.

1) Women's dress John Meyer.

Do. Womans slacks S.S. Kresge.

Do. o Do.

Acetate- Woman's shell. W.T. Grant C0.

D0. Woman's dress Berkshire B-Tween.

Do Woman's shell W.T. Grant Co. camel/15% nylon Womans dress Jule-Wyn.

% cruel/5% nylon. do Hargro.

Do--- Mens shirt Mc Gregor Miracle. Orlon acry Womans sweater... TalbottTaralau. Acrylic.- Boys shirt Garan.

Antron ny Womans slip. Vassarette.

Do do Do. Nylon do S.S. Kresge.

0-- Woman's shell. Cobble Knits. Wool Man's vest Me Gregor Scotch dzWater.

0 Alan Paine. Croslan acrylic Aileen. 75% cotton/25% nylon Do. Cott Do.Do. Do.

- Warner terephthalic acid or a monoperoxy compound of the generalformula positions 4 and 9 is replaced with cetyltrimethylam- After onlytwo cycles (many fewer than the number of times an article of clothingwould be bleached in the home over a period of time) each article wasgraded on a scale from 0 to 3. 0 corresponded to no color change; 1 toslight change; 2 to noticeable change and 3 to damage leaving thearticle unwearable. The value grades from all 32 articles were thenadded to provide a composite color damage indication for eachcomposition tested.

Each composition tested for color damage was also tested for bleachingperformance in a manner similar to that used in the BleachingPerformance Test. AW values after one cycle were ascertained as. in theBleaching Performance Test. It should be noted that the AW valuesBLEACHING TIME AND TEMPERATURE TEST Composition Nos. 10, 11 and 13 ofTable I are placed in bleaching solutions in the componentconcentrations described in Table IV.

TABLE IV Concentrated composition number 10 11 13 Component-solutionconcentration, p.p.m.:

Potassium monopersuliate (ppm. av. 02).-. 53 45 Sodium hypochlorite(p.p.m. av. C12) 200 Cetyltrimethylammonium chloride (pipini. i

Eicosyltrimethylammonium chloride (p.p.m.) Sodium chloride (p.p.m.)Copper sulfate (M X1O- Initial solution pH- Bleaching of these solutionswas then tested at various solution temperatures and performancerecorded over periods of bleaching time. Results are summarizedgraphically in the drawing. The composition of the in vention (No.performs significantly better than monopersulfate alone (No. 13) andcompares favorably with highly concentrated NaOCl (No. 11).

FABRIC SOFT ENING TEST Softening was tested under standard U.S.conditions of 125 F. wash (7 gr./gal. hardness) followed by 100 F. rinsewith 7 gr./gal. hardness. Loads were washed in the automatic mini washerusing 0.9 cup Tide, 1 /2 gallons of water and a 5 /2 pound loadequivalent. The standard load contained 4 terry wash cloths.Compositions were tested for two cycles, and the terry cloths weregraded by a panel of 5 expert judges using the method of round robinpaired comparisons.

The softness of the fabrics treated with Composition N0. 10 (Table IIconcentration) was judged to be signifi cantly greater than the Tidecontrol, Substantially similar results are obtained with CompositionsNos. 3 and 9.

What is claimed is:

1. A dry bleach and fabric-softening composition consisting essentiallyof:

(A) from about 8% to about 60% by weight of a bleaching agent selectedfrom the group consisting of (1) sodium monopersulfate, (2) potassiummonopersulfate, (3) an organic peroxyacid or water-soluble salt thereof,said peroxyacid having the general formula wherein R is selected fromthe group consisting of alkylene groups containing from 1 to about 16carbon atoms and arylene groups containing from 6 to about 8 carbonatoms and Y is a group providing an anionic moiety in aqueous solution,and (4) mixtures thereof; (B) from about 10% to about 60% by weight of aquaternary ammonium compound selected from the group consisting of i Brfillband of alkyl groups containing from about 1 to 3 carbon atoms, arylgroups containing from about 6 to 8 carbon atoms, cycloalkyl groupscontaining from about 5 to 8 carbon atoms, carboxymethyl groups, alkarylgroups containing from about 7 to 10 carbon atoms, pyridyl, and groupsof the general formula wherein a and b are integers and a+b is.-1 to 50;R has the definition of the R R and R groups or is H; R-, is selectedfrom the group consisting of alkylene groups containing 1 to 3 carbonatoms, arylene groups containing 5 to 8 carbon atoms and groups of theformula wherein X is selected from the group consisting of chloride,fluoride, nitrate, sulfate, methylsulfate, carbonate, chlorate, hydrogenphosphate, dihydrogen phosphate and hydroxide; and wherein n is 1 when Xis monovalent and n is 2 when X is divalent;

(C) from about 10% to about by weight of a buffering agent effective tomaintain a solution pH of from about 7 to about 10 when said compositionis dissolved in water for bleaching;

said composition containing sufiicient chloride sa to provide from about5 to about grams of ioniza le chlorine per kilogram of the totalcomposition.

2. The composition of claim 1 wherein the bleaching agent is potassiummonopersulfate.

3. A composition in accordance with claim 1 wherein the bleaching agentis selected from the group consisting of monoperazelaic acid anddiperazelaic acid.

4. A composition in accordance with claim 1 which contains in additionfrom about 0.08% to about 8% by weight of a water-soluble salt of atransition metal element.

5. A composition in accordance with claim 1 which contains from about 2%to about 10% of a water-soluble alkali metal or alkaline earth metalchloride.

6. A composition in accordance with claim 1 wherein the quaternaryammonium compound is a mixture containing from about 2% to about 10% byweight of the total composition of an eicosyltrimethylammonium 'compoundand about 8% to about 30% by weight of the total composition of acetyltrimethylor octadecyltrimethyl-ammonium compound.

7. A concentrated, dry bleach and fabriosoftening composition consistingessentially of:

(A) from about 8% to about 60% by weight of a bleaching agent selectedfrom the group consisting of (1) sodium monopersulfate, Y (2) p m" ln nn rt ai e,--

(B) from about 10% to about 60% by Weight of a quaternary ammoniumcompound selected from the group consisting of wherein R is an alkylgroup containing from 12 to about 20 carbon atoms; R; is selected fromthe group consisting of alkyl groups containing from about 1 to 14carbon atoms, cycloalkyl groups containing from about to 8 carbon atoms,carboxymethyl groups, aryl groups containing from about 6 to 8 carbonatoms, alkaryl groups containing from about 7 to carbon atoms, pyridyland groups of the general formula --(C H O) (C H O) I-l wherein a and bare integers and a+b is 1 to 50; R R and R are each selected from thegroup consisting of alkyl groups containing from about 1 to 3 carbonatoms, cycloalkyl groups containing from about 5 to 8 carbon atoms,carboxymethyl groups, aryl groups containing from about 6 to 8 carbonatoms, alkaryl groups containing from about 7 to 10 carbon atoms,pyridyl, and groups of the general formula H; R7 is selected from thegroup consisting of alkylene groups containing 1 to 3 carbon atoms,arylene and 16 groups containing 5 to 8 carbon atoms and groups of theformula wherein X is selected from the group consisting of chloride,fluoride, nitrate, sulfate, methylsulfate, carbonate, chlorate, hydrogenphosphate, dihydrogen phosphate and hydroxide; and wherein n is 1 when Xis monovalent and n is 2 when X is divalent;

(C) from about 1% to 15% of a water-soluble alkali metal or alkalineearth chloride;

(D) from about 0.08% to about 8% by weight of a water-soluble salt of atransition metal element; and

(E) from about 10% to about by Weight of a buffering agent effective tomaintain a solution pH of from about 7 to about 10 when said compositionis dissolved in water for bleaching; said composition containingsuflicient chloride salt to provide from about 5 to about 100 grams ofionizable chlorine per kilogram of the total composition.

8. A composition in accordance with claim 7 wherein the bleaching agentis selected from the group consisting of diperazelaic acid,diperoxyisophthalic acid, diperoxyterephthalic acid, 4chlorodiperoxyphthalic acid, the monosodium salt of diperoxyterephthalicacid and a monoperoxy compound of the general formula wherein R is analkyl group of from about 8 to about 18 carbon atoms and wherein X and Yare each selected from the group of cations consisting of hydrogen,sodium, potassium, ammonium and substituted ammonium cations.

References Cited UNITED STATES PATENTS 3,360,470 12/1967 WiXon 252993,048,546 8/1962 Lake 252- 3,353,902 11/1967 Diamond 252-8.8

MAYER WEINBLATI', Primary Examiner U.S. Cl. X.R.

8-108, lll; 2528.75, 8.8, 99

237 3 UNITED STATES mm OFFICE CERTIFICATE OF CORRECTION 293mm: 7 Dated y311 197.3

C John Paul Jones and Charles H. Nicol It is certified that errorappears in the aboveidentified patent and that said Letters Patent arehereby corrected as shown below:

Column 4, line 47, delete "miscslles" and insert therefor .1

-- micelles Column 4, line 51, delete "virture" and insert 'thereforvirtue Column 4, line 57, delete "chloride! vand insert thereforchlorine Column 5, line 50, delete '"aproximately" and insert thereforapproximately Column ,5, line 70, delete "'othe" and insert thereforother Column 7, line 13, delete" "hydrogen" and insert therefordihydrogen Column 7, line 22, delete "[C N(CH Column 7, line 53, delete"Consqeuntly" and insert therefor Consequently Column 8, line 50, delete"Transistion" and insert therefor Transition Column 8, line 64,, delete"necessaary" and insert therefor necessary Column 9, line 37, after"Test" replace the period with a comma.

Table I, after "Cetyltrimethylammonium" delete "choride" and inserttherefor chloride HPO and insert therefo:

mow UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 23m V l Dated!Ju ly 31 19 73 g'f John Paul Jones and Charles H. Nicol Page 2 It iscertified that error appears in the aboveidentified patent and that saidLetters Patent are hereby corrected as shown below:

Table II after Diperazelaic acid" delete "Q and insert therefor 0 Column15, line 16 delete "R and insert therefor R Signed and se e this 1stdayof January 1974.

(SEAL) Attest 5 EDWARD M. FLETCHER,JR. RENE D. TEGTMEYER AttestingOfficer 7 Acting Commissioner of Patents

